EP3130394B1 - Coated ptfe membrane - Google Patents

Coated ptfe membrane Download PDF

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Publication number
EP3130394B1
EP3130394B1 EP16170377.2A EP16170377A EP3130394B1 EP 3130394 B1 EP3130394 B1 EP 3130394B1 EP 16170377 A EP16170377 A EP 16170377A EP 3130394 B1 EP3130394 B1 EP 3130394B1
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EP
European Patent Office
Prior art keywords
membrane
fluid
pfsa
coating
porous ptfe
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EP16170377.2A
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German (de)
English (en)
French (fr)
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EP3130394A1 (en
Inventor
Amarnauth Singh
Andrew T. Sitterer
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Pall Corp
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Pall Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/08—Polysulfonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/02—Hydrophilization
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes

Definitions

  • PTFE membranes particularly expanded PTFE (ePTFE) membranes
  • ePTFE expanded PTFE
  • porous PTFE membranes that exhibit metal scavenging or metal removal efficiency while providing low flow resistance.
  • US patent 4,470,859 discloses a method for forming a hydrophilic coating upon a porous substrate such as a reticulate electrode or a filter from a dispersed, perfluorocarbon copolymer.
  • the perfluorocarbon copolymer is dispersed in a solvating medium, a substantial portion, but not necessarily all of the perfluorocarbon being solvated.
  • the dispersion is applied to the substrate and the dispersion medium is removed.
  • the invention relates to a method for filtering a fluid as defined in claim 1.
  • the invention further relates to a porous PTFE membrane comprising a porous PTFE substrate as set out in claim 4.
  • the invention relates to a method of making a metal-removing membrane as set out in claim 5.
  • An embodiment of the invention provides a porous PTFE membrane comprising a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm).
  • PFSA perfluorosulfonic acid
  • a method for filtering a metal-containing fluid comprising passing a metal-containing fluid through a porous PTFE membrane comprising a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm) and removes metal from the fluid.
  • PFSA perfluorosulfonic acid
  • a method for filtering a sulfuric perioxide mixture (SPM) fluid comprising passing the fluid through a porous PTFE membrane comprising a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm) and removes particles from the fluid.
  • SPM sulfuric perioxide mixture
  • Devices including the membranes, and methods of making the membranes, are also provided in accordance with embodiments of the invention.
  • a porous PTFE membrane comprises a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm).
  • PFSA perfluorosulfonic acid
  • a method for filtering a metal-containing fluid comprises passing a metal-containing fluid through a porous PTFE membrane comprising a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm) and removes metal from the fluid (e.g., removing Group 2 metals (e.g., Mg and/or Ca), polyvalent metals and/or transition metals (e.g., Cr, Mn, Fe, and/or Ni) from the metal-containing fluid).
  • PFSA perfluorosulfonic acid
  • a method for filtering a sulfuric perioxide mixture (SPM) fluid comprising passing the fluid through a porous PTFE membrane comprising a porous PTFE substrate having a non-crosslinked coating comprising perfluorosulfonic acid (PFSA) polymer, wherein the membrane has a CWST of at least about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm) and removes particles (such as silica-containing particles) from the fluid.
  • SPM sulfuric perioxide mixture
  • a method of making a metal-removing membrane comprising coating a porous PTFE substrate with a coating comprising perfluorosulfonic acid (PFSA) polymer, as set out in claim 5.
  • PFSA perfluorosulfonic acid
  • the method comprises coating a porous PTFE substrate with a coating comprising perfluorosulfonic acid (PFSA) polymer, wherein a cross-linking agent is not used, and the coating is prepared at room temperature; and curing the coating at a temperature from about 25 °C to about 200 °C.
  • PFSA perfluorosulfonic acid
  • membranes according to the invention can be prepared with a metal agent free coating.
  • membranes can be prepared according to the invention in a manufacturing friendly process, e.g., the preparation can be easily incorporated into existing manufacturing processes, resulting in increased speed of preparation.
  • coated porous PTFE membranes according the invention advantageously provide a combination of high metal scavenging or metal removal efficiency and low flow resistance, while remaining wet in the fluid being processed (i.e., the membranes are non-dewetting in the process fluid) and are useful in a wide range of liquid, and gas (including air) filtration applications, including sterile filtration applications.
  • Exemplary applications include for example, diagnostic applications (including, for example, sample preparation and/or diagnostic lateral flow devices), ink jet applications, lithography, e.g., as replacement for HD/UHMW PE based media, filtering fluids for the pharmaceutical industry, metal removal, production of ultrapure water, treatment of industrial and surface waters, filtering fluids for medical applications (including for home and/or for patient use, e.g., intravenous applications, also including, for example, filtering biological fluids such as blood (e.g., virus removal)), filtering fluids for the electronics industry (e.g., filtering photoresist fluids in the microelectronics industry and hot sulfuric perioxide mixture (SPM) fluids), filtering fluids for the food and beverage industry, beer filtration, clarification, filtering antibody- and/or protein-containing fluids, filtering nucleic acid-containing fluids, cell detection (including in situ ) , cell harvesting, and/or filtering cell culture fluids.
  • diagnostic applications including, for example,
  • porous membranes according to embodiments of the invention can be used to filter air and/or gas and/or can be used for venting applications (e.g., allowing air and/or gas, but not liquid, to pass therethrough).
  • Porous membranes according to embodiments of the inventions can be used in a variety of devices, including surgical devices and products, such as, for example, ophthalmic surgical products.
  • the inventive membranes are dimensionally stable.
  • the porous PTFE membranes can be utilized individually, e.g., as unsupported membranes, and in other embodiments, the porous PTFE membranes can be combined with other porous elements and/or another component, to provide, for example, an article such as a composite, a filter element, and/or a filter.
  • SSC Short Side Chain
  • SFVE Sulfonyl Fluoride Vinyl Ether
  • the ionomer dispersions contain its sulfonic acid form.
  • Another example of a suitable PFSA polymer dispersion is a DuPont TM Nafion ® PF
  • the concentration of PFSA in the coating solution can be varied for different applications.
  • the concentration is in the range of from about 0.1% to about 3%, preferably, in the range of from about 0.12% to about 2.2%.
  • porous PTFE substrates and membranes can be coated in accordance with the invention.
  • Membranes and substrates can be coated as known in the art, for example, but not limited to, dip coating or spraying.
  • the membranes can have any suitable pore structure falling under the scope of the appended claims e.g., a pore size (for example, as evidenced by bubble point, or by K L as described in, for example, U.S. Patent 4,340,479 , or evidenced by capillary condensation flow porometry), a mean flow pore (MFP) size (e.g., when characterized using a porometer, for example, a Porvair Porometer (Porvair pic, Norfolk, UK), or a porometer available under the trademark POROLUX (Porometer.com; Belgium)), a pore rating, a pore diameter (e.g., when characterized using the modified OSU F2 test as described in, for example, U.S. Patent 4,925,572 ), or removal rating media.
  • the pore structure used depends on the size of the particles to be utilized, the composition of the fluid to be treated, and the desired effluent level of the treated fluid.
  • coated porous PTFE membranes according to the invention have pores of diameter in the range of from 1 nm to 100 nm.
  • the coated membrane has a thickness in the range of from about 0.2 to about 5.0 mils (about 5 to about 127 microns), preferably, in the range of from about 0.5 to about 1.0 mils (about 13 to about 25 microns), though membranes can be thicker or thinner than those values.
  • the porous membrane has a critical wetting surface tension (CWST, as defined in, for example, U.S. Patent 4,925,572 ) of at least about 30 dynes/cm (about 30 x 10 -5 N/cm).
  • CWST can be measured by relying on a set of solutions of certain composition. Each solution has specific surface tension. The solution's surface tension ranges from 25 to 92 dynes/cm in small non-equivalent increments.
  • To measure the membrane surface tension the membrane is positioned on to top of white light table, one drop of a solution of certain surface tension is applied to the membrane surface and the time the drop takes to penetrate through the membrane and become bright white as an indication of light going through the membrane is recorded.
  • the CWST can be selected as is known in the art, e.g., as additionally disclosed in, for example, U.S. Patents 5,152,905 , 5,443,743 , 5,472,621 , and 6,074,869 .
  • the coated PTFE membrane has a CWST of at least about 30 dynes/cm (about 30 x 10 -5 N/cm), and in some embodiments, at least about 35 dynes/cm (about 35 x 10 -5 N/cm).
  • the coated PTFE membrane may have a CWST in the range of from about 30 dynes/cm (about 30 ⁇ 10 -5 N/cm) to about 40 dynes/cm (about 40 ⁇ 10 -5 N/cm), or more.
  • An article such as a filter, filter element and/or composite including the coated porous PTFE membrane can include additional elements, layers, or components, that can have different structures and/or functions, e.g., at least one of any one or more of the following: prefiltration, support, drainage, spacing and cushioning.
  • the filter can also include at least one additional element such as a mesh and/or a screen.
  • the membrane can have a variety of configurations, including planar, pleated, spiral, and/or hollow cylindrical.
  • the membrane, filter element, composite and/or filter is typically disposed in a housing comprising at least one inlet and at least one outlet and defining at least one fluid flow path between the inlet and the outlet, wherein the membrane is across the fluid flow path, to provide a filter device.
  • the membrane, composite and/or filter is disposed in a housing comprising at least one inlet and at least two outlets and defining at least a first fluid flow path between the inlet and the first outlet, and a second fluid flow path between the inlet and the second outlet, wherein the membrane is across the first fluid flow path, to provide a filter device.
  • the filter device may be sterilizable. Any housing of suitable shape and providing at least one inlet and at least one outlet may be employed.
  • the housing can be fabricated from any suitable rigid impervious material, including any impervious thermoplastic material, which is compatible with the fluid being processed.
  • the housing can be fabricated from a metal, such as stainless steel, or from a polymer.
  • the housing is a polymer, such as an acrylic, polypropylene, polystyrene, or a polycarbonated resin.
  • This example demonstrates a method of preparing a membrane according to an embodiment of the invention.
  • a 0.25% PFSA solution (AQUIVION PFSA 24; D83-24B Solvay Plastics) is prepared in a methanol-water medium to obtain a polymer solution.
  • a commercially available PTFE substrate ((membrane) Sumitomo Electric Fine Polymer, Inc., nominal pore size 50 nm) is dip-coated with the polymer solution until fully wet, removed from the solution and drained for about 2 minutes, and restrained and dried at 150 °C for 10 minutes followed by washing in room temperature DI water for 12 hours, and tested.
  • results are as follows: Media Untreated PTFE Commercially available UV treated PTFE PFSA coated PTFE CWST (dynes/cm) 27 32 35 Flow (L/min/ft 2 /psid) 1.07 1.16 0.88 IPA K L , Water K L (psi) 46.7, NA 48.2, 51.5 57.3, 35.5 SPM CWST (dynes/cm) 27 32 35
  • This example shows CWST is increased (thus, the membrane is non-dewetting), with little reduction in flow, in accordance with an embodiment of the invention.
  • This example shows the metal removal efficiencies for two PFSA coated PTFE membranes (prepared with different concentrations of PFSA) according to embodiments of the invention, compared to an untreated (control) PTFE membrane, and a commercially available UV treated PTFE membrane.
  • Two PFSA coated PTFE membranes are prepared as generally described in Example 1, wherein one membrane is dip-coated in a 0.25% PFSA solution (AQUIVION PFSA D83-24B) prepared in a methanol-water medium, and another membrane is dip-coated in a 0.5% PFSA solution (AQUIVION PFSA D83-24B) prepared in a methanol-water medium.
  • the fluid samples separately contain the following metals: Li, Na, K (Group 1 metals); Mg, Ca (Group 2 metals); Al, Pb (Group 3 metals), and Cr, Mo, Mn, Fe, Ni, Cu, Zn (Transition metals).
  • embodiments of membranes according to the invention as compared to an untreated membrane and a commercially available UV treated membrane, efficiently remove various Group 2 metals and various transition metals.
  • This example shows the metal removal efficiencies for two PFSA coated PTFE membranes (prepared with different concentrations of PFSA) according to embodiments of the invention.
  • Two PFSA coated PTFE membranes are prepared as generally described in Example 1, wherein one membrane is dip-coated in a 0.25% PFSA solution (AQUIVION PFSA D83-24B) prepared in a methanol-water medium, and another membrane is dip-coated in a 0.5% PFSA solution (AQUIVION PFSA D83-24B) prepared in a methanol-water medium.
  • the fluid samples separately contain the following metals: Li, Na, K (Group 1 metals); Mg, Ca (Group 2 metals); Al, Pb (Group 3 metals), and Cr, Mo, Mn, Fe, Ni, Cu, Zn (Transition metals).
  • This example shows the PFSA coating on the PTFE membrane is not cross-linked, as the coating is not removed by soaking in solvent.
  • PTFE membranes are weighed using a 7 digit balance.
  • Membranes are coated using a 24% w/w (stock) PFSA solution as generally described in Example 1 to provide non-cross-linked membranes.
  • Cross-linked membranes are prepared using a 24% w/w (stock) PFSA solution, wherein the membranes are dried at about 260 °C.
  • the dried control, non-cross-linked, and cross-linked membranes are weighed.
  • the membranes are soaked in the same solvent (methanol) solution used to make the coated membranes.
  • One set of coated membranes is soaked in room temperature solvent solution, another set of coated membranes is soaked in 40 °C solvent solution.
  • 40 °C solvent solution helps speed up solvation of any byproduct.
  • the membranes are rinsed in fresh solvent 3 times, dried, and weighed again.
  • the weights of the control membrane and the non-cross-linked coated membrane soaked in room temperature and 40 °C solvent solutions are the same as the original weights, while the weights of the cross-linked coated membranes soaked in room temperature and 40 °C solvent solutions are less than the original weight, showing that the membrane is cross-linked.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Nanotechnology (AREA)
EP16170377.2A 2015-07-31 2016-05-19 Coated ptfe membrane Active EP3130394B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14/814,996 US20170028359A1 (en) 2015-07-31 2015-07-31 Coated ptfe membrane

Publications (2)

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EP3130394A1 EP3130394A1 (en) 2017-02-15
EP3130394B1 true EP3130394B1 (en) 2023-10-25

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US (1) US20170028359A1 (zh)
EP (1) EP3130394B1 (zh)
JP (1) JP6295456B2 (zh)
KR (1) KR20170015118A (zh)
CN (1) CN106390778A (zh)
SG (1) SG10201603824PA (zh)
TW (1) TWI637988B (zh)

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Publication number Priority date Publication date Assignee Title
US10322379B2 (en) 2014-07-21 2019-06-18 Ohio State Innovation Foundation Composite membranes for separation of gases
US20170028361A1 (en) * 2015-07-31 2017-02-02 Pall Corporation Ptfe/pfsa blended membrane
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JP2022018727A (ja) * 2020-07-16 2022-01-27 住友化学株式会社 ガス分離膜及びその製造方法

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JP2012183237A (ja) * 2011-03-07 2012-09-27 Kaneka Corp 新規白血球除去フィルター
US20130112621A1 (en) * 2011-11-03 2013-05-09 Lei Zheng Water filtration article and related methods

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CN106390778A (zh) 2017-02-15
US20170028359A1 (en) 2017-02-02
SG10201603824PA (en) 2017-02-27
KR20170015118A (ko) 2017-02-08
TW201704306A (zh) 2017-02-01
JP6295456B2 (ja) 2018-03-20
EP3130394A1 (en) 2017-02-15
JP2017029975A (ja) 2017-02-09

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